Breaking Global Diatropic Current to Tame Diradicaloid Character: Thiele's Hydrocarbon Under Macrocyclic Constraints

Author:

Banachowicz Piotr1,Das Mainak1,Kruczała Krzysztof1,Siczek Miłosz2,Sojka Zbigniew1,Kijewska Monika2,Pawlicki Miłosz1ORCID

Affiliation:

1. Faculty of Chemistry Jagiellonian University Gronostajowa 2 30-387 Kraków Poland

2. Department of Chemistry University of Wrocław F. Joliot-Curie 14 50383 Wrocław Poland

Abstract

AbstractA diradical/biradical character of organic derivatives is one of the key aspects of contemporary research focusing on the fundamental studies followed by potential applicability relying on the unique optical, electronic, or magnetic properties assigned to unpaired electrons. A precise involvement of two p‐phenylenes into a cyclophane‐like conjugated, diatropic system creates a flexible molecule with the two different characters of both subunits (benzene and quinone) imprinting into the structure a Kekulé delocalized system. A dynamic of both carbocyclic subunits, and their mutual interaction generates a singlet open‐shell state (J=−1.25 kcal/mol) as documented spectroscopically (NMR and EPR). The extended theoretical analysis has proved a correlation between dihedral angle and the diradicaloid character that shifts from a closed‐shell singlet to an open‐shell state, eventually showing the y0=0.86 for 78 degrees and ΔEST=−0.34 kcal/mol.

Publisher

Wiley

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